A novel type of N-formylation and related reactions of amines via cyanides and esters as formylating agents

Abstract

A novel N-formylation and related reactions proceed from cyanides promoted by esters.

N3-[(E)-Morpholin-4-ylmethylidene]-1-phenyl-1H-1,2,4-triazole-3,5-diamine monohydrate

“…This reaction is analogous to the previously described intramolecular heterocyclizations of N-substituted aminomethylene malonates (Sunder & Peet, 1980;Yamazaki et al, 1988;Selic et al, 1998Selic et al, , 2000Tkachev et al, 2007). However, we could find the intermolecular variant of the reaction in two publications (Rajappa et al, 1970;Bao et al, 2008), only. Good yields of the compounds 3 allow to expect that the reaction will be a useful tool for the selective synthesis of N-hetaryl substituted formamidines.…”

“…Intramolecular reactions of N-substituted aminomethylene malonates accompanied by nucleophilic substitution of malonic ester were described by Sunder & Peet (1980); Yamazaki et al (1988); Selic et al (1998Selic et al ( , 2000; Tkachev et al (2007). Analogous intermolecular reaction affording substituted formamidines was described by Rajappa et al (1970); Bao et al (2008). For examples of the use of the triazolyl-substituted amidines in the synthesis of annulated heterocycles, see: Dolzhenko et al (2007Dolzhenko et al ( , 2008a.…”

A capable cobalt nano‐catalyst for the N‐formylation of various amines and its biological activity studies

“…Several synthetic methods have been reported for the N ‐formylation reactions, but most of them are suffering from some disadvantages such as the harsh reaction condition, in situ formation of harmful, toxic and corrosive materials, long reaction times, use of relatively high temperature, relatively low yields, difficulties in preparation of the catalyst, formation of by‐product and impurities, hard work‐up, use of homogeneous catalyst which cannot easily be recovered and reused, and the use of expensive catalyst …”

Carbon Nanotube–Gold Nanohybrid Catalyzed N‐Formylation of Amines by using Aqueous Formaldehyde

“…Formamides have been extensively employed in Vilsmeier formylation5, 6 and as key amino protecting groups in peptide synthesis 6. 7 The formylation of various amines has been reported with reagents such as formic acid/amide,1, 8 acetic formic anhydride,9 formate,10 cyanide,11 and chloral 12. However, the wide applicability of these methods has been curtailed by one or more shortcomings such as undesirable side reactions, the toxicity of the reagents, the requirement for the pre‐preparation of the formylating agents, elevated temperatures, and anhydrous conditions.…”